CN110289391B - Metal lithium alloy and preparation method and application thereof - Google Patents
Metal lithium alloy and preparation method and application thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a metal lithium alloy and a preparation method and application thereof, wherein the preparation method comprises the following steps: extracting alkali metal salt solid from the lithium ore leaching solution or the purified lithium brine; drying the alkali metal salt solid; carrying out vacuum reduction on the dried alkali metal salt solid under vacuum, and condensing to obtain a metal lithium alloy; wherein the reducing agent used for vacuum reduction is one or two of aluminum powder, silicon powder, magnesium powder and calcium powder, and the reduction temperature is 700-1300 ℃. The preparation method of the lithium alloy provided by the invention has simple process and convenient operation, and when the prepared lithium alloy is used as a negative electrode, the side reaction with electrolyte can be relieved, the current concentration effect can be eliminated, the generation of dendritic crystals is inhibited, and the coulomb efficiency, the specific capacity and the cycling stability of the lithium metal battery are improved.
Description
Technical Field
The invention relates to the field of metallurgical physical chemistry, in particular to a metal lithium alloy and a preparation method and application thereof.
Background
Lithium is an important "energy metal" and is known as the strategic element of the 21 st century in the united states. The total reserve of lithium resources which is proved in China occupies the second place of the world and mainly exists in the form of salt lake brine and ores. With the rise of lithium ion batteries, the demand for lithium resources is increasing. The traditional method for extracting lithium from lithium ore cannot meet the social requirements, and the process of extracting lithium resources from salt lake brine becomes a necessary trend for developing lithium resources in China.
With the well-blowout type growth of social energy requirements, the lithium ion battery is inherently limited and is difficult to meet the social requirements. Research on a new generation of high energy secondary battery is imminent. The metallic lithium is the lightest metal and has the density of only 0.534g/cm3The theoretical specific capacity is higher than 3860 mAh/g. Lithium-sulfur batteries (Li-S) and lithium-air batteries, which use metallic lithium as the negative electrode, have attracted considerable attention because of their high capacity. Lithium cathodes have become a unique choice for high energy battery systems.
However, lithium metal produces lithium dendrites during cycling, which grow and eventually pierce the separator, causing serious safety problems. In addition, when the metallic lithium is exfoliated, "dead lithium" is formed, causing irreversible loss of capacity. Secondly, metallic lithium is very reactive and reacts with almost all components in the electrolyte to form a complex solid electrolyte interface.
In order to solve the problems of the Lithium cathode and realize the application of the Lithium metal secondary battery with high Energy density as early as possible, the Lithium arsenic, Lithium selenium and Lithium bismuth alloy is prepared by the beam night of the university of Hunan (X.Liang, et al.A. simple Surface Chemistry Route to a stabilized Lithium metal anode, Nature Energy,2017,2,17119 and 17126), the activity of the Lithium metal is reduced, the alloy element is used as an active site for Lithium deposition, the Lithium can be induced to be uniformly deposited, and the service life of the Lithium metal battery is prolonged. However, this alloying method is not easy to realize, and large-scale production is not possible, and the inherent problems of metallic lithium cannot be fundamentally solved. The preparation of lithium alloys by simpler methods is undoubtedly of particular importance for the development of lithium metal batteries.
Disclosure of Invention
The invention provides a preparation method and application of a metal lithium alloy, and aims to prepare the metal lithium alloy by a simple and effective method, reduce the activity of lithium, relieve the side reaction of a lithium alloy cathode and an electrolyte and improve the cycle stability, coulombic efficiency and specific capacity of a lithium metal battery.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a metal lithium alloy comprises the following steps:
1) extracting alkali metal salt solid from the lithium ore leaching solution or the purified lithium brine;
wherein the alkali metal salt solids include lithium salt solids, sodium salt solids, potassium salt solids, rubidium salt solids, and cesium salt solids;
2) drying the alkali metal salt solid obtained in the step 1);
3) carrying out vacuum reduction on the dried alkali metal salt solid, and condensing to obtain a metal lithium alloy;
wherein the reducing agent used for vacuum reduction is one or two of aluminum powder, silicon powder, magnesium powder and calcium powder, and the reduction temperature is 700-1300 ℃.
Preferably, the concentration ratio of lithium to magnesium and the concentration ratio of lithium to boron in the lithium ore leaching solution or the purified lithium brine in the step 1) are both greater than 1.
Preferably, the content of alkali metal in the lithium ore leaching solution or the purified lithium brine obtained in the step 1) is more than 10 mg/L.
Preferably, the alkali metal salt solid is prepared by the following method: and (3) carrying out countercurrent extraction and liquid separation on the lithium ore leaching solution or the purified lithium brine by using a composite extractant, and evaporating the organic solvent to obtain lithium salt solids and other alkali metal salt solids.
More preferably, the composite extracting agent comprises a lithium extraction extracting agent and an alkali metal extracting agent except for lithium extraction;
the lithium extraction extractant comprises an acidic extractant and a neutral complexing lithium extraction extractant, the acidic extractant comprises bis (trifluoromethanesulfonimide) and/or perchloric acid, and the neutral complexing lithium extraction extractant comprises one or more of NN-dimethylacetamide, tributyl phosphate, dibutyl butyl phosphate and dibutyl phosphate;
the other alkali metal extractants except for extracting lithium comprise one or more of phenol alcohols, crown ethers, biternamine derivatives and biternamine borides, and the solvent used by the other alkali metal extractants except for extracting lithium is a carbonate organic solvent or an ether organic solvent.
Preferably, the alkali metal salt solid can also be prepared by the following method: adding a composite precipitator into the lithium ore leaching solution or the purified lithium brine to separate out lithium salt and other alkali metal salt in a solid form, and then filtering and drying to obtain alkali metal salt solid.
More preferably, the composite precipitant includes a lithium ion precipitant and a precipitant of an alkali metal other than lithium;
the lithium ion precipitator is carbonate, and the precipitator of alkali metals except lithium is one or more of complex acid salt, heteropoly acid, alum and halide.
Based on the same inventive concept, the invention also provides a metal lithium alloy prepared by the preparation method.
Based on the same invention concept, the invention also provides a lithium metal cathode which is directly formed by directly punching the lithium metal alloy prepared by the method into sheets. Preferably, the lithium metal alloy is directly punched into a lithium alloy sheet with the diameter of 14mm to be used as the metal lithium negative electrode.
Based on the same inventive concept, the invention also provides a lithium battery comprising the metal lithium cathode.
The scheme of the invention has the following beneficial effects:
(1) the preparation method of the lithium alloy provided by the invention has low requirements on equipment, is a simple, efficient, practical and low-cost method, and the obtained alloy has high purity and does not pollute the environment in the production process.
(2) The lithium alloy prepared by the preparation method of the lithium alloy can reduce the activity of lithium in the lithium alloy, can relieve the side reaction with electrolyte when the lithium alloy is taken as a negative electrode, reduces the loss of active substance lithium, can eliminate the current concentration effect by taking the lithium alloy as a framework and a lithium deposition active site, inhibits the generation of dendritic crystals, and improves the coulombic efficiency, specific capacity and cycling stability of the lithium metal battery.
(3) The purity of the lithium alloy prepared by the embodiment is as high as more than 99%, and the impurity content is low. The prepared lithium metal battery can stably circulate for more than 270 circles, the specific capacity is more than 150mAh/g, and the average coulomb efficiency is more than 99%.
Drawings
Fig. 1 is a voltage curve of a lithium metal battery according to example 1 of the present invention;
fig. 2 is a plot of coulombic efficiency versus cycle number for a lithium metal battery of example 2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The preparation method of the metal lithium alloy provided by the invention comprises the following steps:
1) extracting alkali metal salt solid from the lithium ore leaching solution or the purified lithium brine;
wherein the alkali metal salt solids include lithium salt solids, sodium salt solids, potassium salt solids, rubidium salt solids, and cesium salt solids;
2) drying the alkali metal salt solid obtained in the step 1);
3) carrying out vacuum reduction on the dried alkali metal salt solid, and condensing to obtain a metal lithium alloy;
wherein the reducing agent used for vacuum reduction is one or two of aluminum powder, silicon powder, magnesium powder and calcium powder, and the reduction temperature is 700-1300 ℃.
In the step 1), the concentration ratio of lithium to magnesium and the concentration ratio of lithium to boron in the purified lithium brine or lithium ore leachate are both greater than 1, and the content of alkali metal is greater than 10 mg/L.
The preparation method of the alkali metal salt solid comprises the following steps: carrying out countercurrent extraction on the purified lithium ore leachate or the purified salt lake brine by using the composite extractant, separating liquid to obtain organic solution containing lithium and other alkali metal salts, then adding hydrochloric acid for carrying out back extraction, separating liquid to obtain aqueous solution containing lithium and other alkali metal chloride salts, evaporating water, and then evaporating the organic solvent to obtain alkali metal salt solid; the composite extractant is an acidic lithium extraction extractant such as bistrifluoromethane sulfimide and perchloric acid; the neutral complexing lithium extraction is a lithium ion extraction agent of NN-dimethylacetamide, tributyl phosphate, dibutyl butyl phosphate and dibutyl butyl phosphate. The composite extractant also comprises other alkali metal ion extractants, such as phenol alcohols, crown ethers, bispicramine and derivatives thereof, borides and the like. Of these, phenols are preferable, and 4-tert-amyl-2- (. alpha. -methylbenzyl) phenol (t-BAMBP) or 4-sec-butyl-2- (. alpha. -methylbenzyl) phenol (s-BAMBP) is more preferable as the other alkali metal ion extractant.
The preparation method of the alkali metal salt solid can also comprise the following steps: carbonate is taken as a lithium ion precipitator; adding a complexing acid salt, heteropoly acid, alum or halide serving as a precipitator of alkali metals except lithium into the lithium ore leaching solution or purified lithium brine to precipitate lithium ions and other alkali metal ions, and filtering and drying to obtain an alkali metal salt solid.
In the step 3), the vacuum degree is 1-50Pa, and the reaction time is 1-10 h. The atmosphere for the reduction treatment is an inert atmosphere such as nitrogen, helium, argon, neon, argon, hernia, etc.
Example 1
Adding enough 6mol/L HTFSI solution and 2mol/L (t-BAMBP) solvent which is 1, 3-Dioxolane (DOL) into purified concentrated brine of the Qinghai Sitai Ginell salt lake, separating to obtain an organic solution containing LiTFSI and other alkali metal salts, adding 3mol/L hydrochloric acid, performing back extraction on alkali metals to obtain a corresponding alkali metal chloride solution, and evaporating water to obtain a corresponding alkali metal salt solid. Obtaining corresponding alkali metal chloride solution, evaporating water to obtain corresponding alkali metal salt solid.
Then, according to the mass ratio of (lithium salt, sodium salt, potassium salt, rubidium salt and cesium salt): weighing the above substances in a ratio of 1:1, and uniformly mixing and briquetting. Putting into a vacuum reducing furnace, and carrying out vacuum reduction at 700 ℃, wherein the vacuum degree is kept at 1Pa, and the reaction time is 8 h. The obtained product is condensed and cast into flaky lithium sodium potassium rubidium cesium alloy with the diameter of 14mm again, and the alloy purity can reach 99.5%.
The resulting lithium alloy was assembled into a 2032-type symmetrical battery. Electrolyte salt is LiTFSI with 1mol/L, and solvent is DOL (1, 3-dioxolane) and DME (ethylene glycol dimethyl ether), wherein DOL and DM areThe volume ratio of E is 1: 1. The fixed charge-discharge capacity per cycle is 1mAh/cm2The current density is 5mA/cm2. The charge and discharge test of the symmetrical battery under the conditions can stably circulate for 350 circles, the average voltage polarization is 80mV, and the overpotential is very stable.
Example 2
Adding enough 7mol/L HClO into 5L purified lepidolite leaching solution4The solution, and 3mol/L s-BAMBP, the solvent is ethylene glycol dimethyl ether (DME), and 5-stage countercurrent extraction is carried out. Separating to obtain LiClO-containing liquid4And other organic solution of other alkali metal salt, then adding 8mol/L hydrochloric acid, performing back extraction to obtain alkali metal chloride solution, evaporating water, and drying to obtain solid chloride of lithium sodium potassium rubidium cesium.
Then, according to the mass ratio of (lithium salt, sodium salt, potassium salt, rubidium salt and cesium salt): weighing the above substances in a ratio of 2:1, and uniformly mixing and briquetting. Putting into a vacuum reducing furnace, and carrying out vacuum reduction at 1300 ℃ with the vacuum degree kept at 50Pa and the reaction time of 10 h. The obtained product is condensed and cast into flaky lithium sodium potassium rubidium cesium alloy with the diameter of 14mm again, and the alloy purity can reach 99.6%.
Mixing LiFePO4The conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 80:10:10, N-methyl pyrrolidone (NMP) is used as a dispersing agent, the mixture is stirred in a stirrer at the speed of 1200rpm for 1 hour, the obtained slurry is uniformly coated on a carbon-containing aluminum foil of a current collector, and then the carbon-containing aluminum foil is dried in a vacuum box at the temperature of 60 ℃ for 24 hours to be used as a positive electrode. 1mol/L lithium hexafluorophosphate (LiPF) with Celgrad2400 as a separator6) The electrolyte solvent was Ethyl Carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1:1), and the alloy in example 2 was used as a negative electrode to assemble a full cell. Constant current charging and discharging are carried out at 1C multiplying power, and the cut-off voltage is 2.2-4.2V. And the circulation is carried out for 270 times, the capacity reaches 150mAh/g, and the average coulombic efficiency is 99.7 percent.
Example 3
Adding enough 3mol/L HClO into 5L purified lepidolite leaching solution4Solution and solvent are glycol dimethyl ether (DME), and five-stage countercurrent extraction is carried out. Separating to obtain LiClO-containing liquid4Organic solution of (2), evaporationOrganic solvent to obtain LiClO4And (3) a solid. Adding 2mol/L iodine chloride solution into the residual lepidolite leaching solution to obtain NaICl2、KICl2、RbICl2、CsICl2Evaporating the solvent to obtain solid sodium salt, potassium salt, rubidium salt and cesium salt. Then, mixing the following components in percentage by mass (lithium salt, sodium salt, potassium salt, rubidium salt and cesium salt): weighing the above substances in a ratio of 1:1, and uniformly mixing and briquetting. Putting into a vacuum reducing furnace, and carrying out vacuum reduction at 1000 ℃ with the vacuum degree kept at 50Pa and the reaction time of 4 h. The obtained product is condensed and cast into a sheet alloy with the diameter of 14mm again, and the alloy purity can reach 99.4%.
The obtained lithium alloy ingot was cut into lithium alloy sheets having a diameter of 14 mm. And the lithium iron phosphate is assembled into a full cell, a constant current charge and discharge test is carried out at a rate of 1C, the cycle is carried out for 400 times, the capacity is stabilized to be more than 152mAh/g, and the average coulomb efficiency reaches 99.9 percent.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the metal lithium alloy is characterized by comprising the following steps of:
1) extracting alkali metal salt solid from the lithium ore leaching solution or the purified lithium brine;
the alkali metal salt solid is prepared by the following method: performing countercurrent extraction and liquid separation on the lithium ore leaching solution or the purified lithium brine by using a composite extractant, and evaporating an organic solvent to obtain lithium salt solids and other alkali metal salt solids;
or the alkali metal salt solid is prepared by the following method: adding a composite precipitator into the lithium ore leaching solution or the purified lithium brine to separate out lithium salt and other alkali metal salt in a solid form, and then filtering and drying to obtain alkali metal salt solid;
wherein the alkali metal salt solids include lithium salt solids, sodium salt solids, potassium salt solids, rubidium salt solids, and cesium salt solids;
2) drying the alkali metal salt solid obtained in the step 1);
3) carrying out vacuum reduction on the dried alkali metal salt solid, and condensing to obtain a metal lithium alloy;
wherein the reducing agent used for vacuum reduction is one or two of aluminum powder, silicon powder, magnesium powder and calcium powder, and the reduction temperature is 700-1300 ℃.
2. The method according to claim 1, wherein the ratio of lithium to magnesium and lithium to boron in the lithium ore leachate or purified lithium brine obtained in step 1) is greater than 1.
3. The method of claim 1, wherein the alkali metal content of the lithium ore leachate or purified lithium brine obtained in step 1) is greater than 10 mg/L.
4. The method of claim 1, wherein the complex extractant comprises a lithium extraction extractant and a sodium, potassium, rubidium, and cesium extraction extractant;
the lithium extraction extractant comprises an acidic extractant and a neutral complexing lithium extraction extractant, the acidic extractant comprises bis (trifluoromethanesulfonimide) and/or perchloric acid, and the neutral complexing lithium extraction extractant comprises one or more of NN-dimethylacetamide, tributyl phosphate, dibutyl butyl phosphate and dibutyl phosphate;
the sodium, potassium, rubidium and cesium extraction agent comprises one or more of phenol alcohols, crown ethers, biternamine derivatives and biternamine borides, and the solvent used by the sodium, potassium, rubidium and cesium extraction agent is a carbonate organic solvent or an ether organic solvent.
5. The method of making a lithium metal alloy of claim 1, wherein the composite precipitant comprises a lithium ion precipitant and a sodium, potassium, rubidium, and cesium ion precipitant;
the lithium ion precipitator is carbonate, and the sodium ion precipitator, the potassium ion precipitator, the rubidium ion precipitator and the cesium ion precipitator are one or more of complex acid salt, heteropoly acid, alum and halide.
6. A metallic lithium alloy, which is prepared by the preparation method of any one of claims 1 to 5.
7. A lithium metal negative electrode is characterized in that the lithium metal negative electrode is directly formed by directly punching the lithium metal alloy prepared by the preparation method of any one of claims 1 to 5 or the lithium metal alloy prepared by the preparation method of claim 6 into a sheet.
8. A lithium battery comprising the lithium metal negative electrode according to claim 7.
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| US6737017B2 (en) * | 2002-06-14 | 2004-05-18 | General Electric Company | Method for preparing metallic alloy articles without melting |
| US7151069B2 (en) * | 2003-07-16 | 2006-12-19 | Japan Storage Battery Co., Ltd. | Manufacturing processes of catalyst layer for fuel cell |
| CN1269243C (en) * | 2003-09-10 | 2006-08-09 | 中国科学院物理研究所 | Nanometer metal or alloy composite material and preparation and usage thereof |
| JP2005097648A (en) * | 2003-09-22 | 2005-04-14 | Mitsui Mining & Smelting Co Ltd | Method for recovering magnesium-based alloy waste material |
| CN101845559B (en) * | 2010-04-12 | 2011-09-14 | 东北大学 | Device and method for preparing lithium metal by using vacuum metal heat reduction |
| CN102080164A (en) * | 2010-12-02 | 2011-06-01 | 重庆大学 | Method for preparing Mg-Li alloy by vacuum synchronous thermal reduction |
| CN102220502B (en) * | 2011-05-26 | 2012-11-21 | 中国地质科学院矿产综合利用研究所 | Method for preparing aluminum-scandium intermediate alloy by thermal reduction of aluminum-calcium alloy |
| CN103849900B (en) * | 2014-02-25 | 2016-08-17 | 广东省工业技术研究院(广州有色金属研究院) | A kind of preparation method of rare earth alloy |
| CN105274576B (en) * | 2014-05-28 | 2017-12-22 | 奥勇新材料科技（上海）有限公司 | A kind of method that continuous reduction prepares metal in fused-salt medium |
| KR20170101927A (en) * | 2014-12-02 | 2017-09-06 | 더 유니버시티 오브 유타 리서치 파운데이션 | Deoxidation of molten salts of metal powders |
| KR102448293B1 (en) * | 2015-10-02 | 2022-09-28 | 삼성에스디아이 주식회사 | Negative active material, and negative electrode and lithium battery including the material |
| CN105583406B (en) * | 2016-03-29 | 2018-12-11 | 宁夏东方钽业股份有限公司 | A kind of preparation method of low oxygen content metal powder |
| CN109689903B (en) * | 2016-07-06 | 2021-09-24 | 基纳泰克有限公司 | Thermochemical treatment of exothermic metal systems |
| CN106319245B (en) * | 2016-09-19 | 2018-05-04 | 福州大学 | A kind of method that lepidolite successive reaction carries lithium |
| CN108277367B (en) * | 2017-01-06 | 2020-09-18 | 中国科学院过程工程研究所 | Method for extracting lithium from lithium-containing ore |
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| CN109852797B (en) * | 2017-12-16 | 2020-12-29 | 虔东稀土集团股份有限公司 | Extraction solvent for extracting and separating lithium element and method for extracting and separating lithium element by using extraction solvent |
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| CN109811145B (en) * | 2019-04-09 | 2021-04-16 | 北京欧菲金太科技有限责任公司 | Method for preparing metallic lithium from lithium-containing mineral |
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